An alternative macro-Raman mapping algorithm, adapting the numbers of accumulations

Abstract

Macro-Raman mapping is an approach that is well suited to study the distribution of molecules over a surface of typically several cm², such as the pigment distribution on a painting. During such an experiment, thousands Raman spectra are recorded in a predefined array of points. As there can be a huge difference in Raman sensitivity between different molecules, an alternative approach is proposed, where measurement times are adapted according to the quality of the Raman scatterer. Therefore, an iterative process is implemented, involving recording short accumulations, followed by a quick evaluation. As soon as the accumulated spectrum reaches a quality criterium, measurement of the next point is started, while in the other case further accumulations are added. The influence of using multiple accumulations opposite to a single measurement for a prolonged period has been assessed by comparing the overall measurement time and the spectral intensity of the main Raman band (520.5 cm⁻¹) of silicon. Another prerequisite for this algorithm to be successful is the need for a quick and reliable evaluation of the spectral quality. This was examined by applying this function on the accumulations of Raman spectra of 49 paint samples from a colour chart. Finally, the variable-accumulation algorithm is applied during a macro-Raman mapping experiment of a watercolour painting on paper. Despite a significant gain in overall measuring time, this novel approach yields a qualitative data set that can be used for creating clear Raman maps, using different data processing methods.